Process of preparing sulphonic acids of aliphatic ethers of high molecular weight



Patented May '31, 1938 UNITED PROCESS OF PB-EABING SUIIHONIG ACIDS F ALIPHATIC ETHEBS OF HIGH MOLEC- ULAB WEIGHT Edmund Waldmann, Klosternenbnrg, and August Chwala, Vienna, Austria, ors to I. G. Farbenindustrie Aktlengesellschaft, orton-the-Main, Germany No Drawing. Serial No.

. U. s. Application No. 747,250, filed October 6, 1934 in the name of Edmund Waldmann and August Chwala for Wetting, cleansing and dispersing agents and process of preparing them.

We have found that sulphonic acids of aliphatic ethers of high molecular weight are obtainable by acylating at the nitrogen the sulphonic acids of amino others or their salts with fatty acids containing at least 10 carbon atoms in the molecule, naphthenic or resinic acids or the halides or anhydrides of these acids.

. as parent materials for these compounds there are used dihalogenated ethers. 'They are converted into the halogenated ether sulphonic acids by causing them to react with sodium or ammonium 2o sulphite, which is used either in approximately equimolecular or smaller quantities in the solid state or in aqueous alcohol solution, according to the reactivity of the halogen atoms present in the dihalogenated ethers. By heating the halogenated ether sulphonic acids as obtained with ammonia or primary amines, the halogen is replaced by nitrogen with formation of amino-' ether sulphonic acids, which are then acylated at the nitrogen by heating them with a molar 30, quantity of a fatty acid such as oleic acid, palmitlc acid, or by treating them with the chloride of a fatty acid.

By using as dihalogenated ether, for instance, beta-beta-dichlorodiethylether, there are ob- 35 tained:

I t cnnecomcm) CHQCHa-O-CHziCHiSOiNB (CnHmCO- radical of the lauric acid).

Application November '19, 1936, 111,140. In Austria October 7,

6 Claims. (01. 260-124) presence of this group causes. in contrast to similarly constituted compounds which 'do not contain it, an increase in various valuable properties, especially, for instance, an increase in the ability to keep calcium soaps in a colloidal solution.

In the above mentioned reactions there may also be used, as dihalogenated ethers, the condensation products of aldehydes especially formaldehyde, with hydrochloric acid, ior instance, of

the composition:

ClCflz-O-Clhc the condensation products of halogenated monoor polyhydric alcohols with aldehydes, particularly formaldehyde and hydrochloric acid, such as CH2Cl-CI-Iz-O-C 2C1 furthermore the ethers of halogen hydrines of polyhydric alcohols, for example, the methylether of beta-beta-glycerine-dichlorohydrine, and the alkyl ether of peta-erythrlt-di-(or tri-) chlorohydrine CH OC Hi As fatty acids of high molecular weight those containing more than 10- carbon atoms in the molecule are used, for instance, lauric, myristic, palmitic; oleic, linoleic, linolenic or eleostearlc acid. These acids may also be used in the form of natural mixtures.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts are by weight:

(1) 142 grams of dichlorodiethylether (1 mol.) are heated for several hours in an autoclave at 120-130 C. together with 20 grams of NaHS, dissolved in alcohol, with addition of 1-2 grams of potassium iodide.

After cooling, the contents of the autoclave is filtered from the NaCl formed, the alcohol is dis- 'tilled from the water bath and the residue which contains, besides unaltered dichloroether, the chloro-ether-mercaptan formed of the following formula CHiiCl-CWMHi-SH is decomposed into its-components by fractional distillation under reduced pressure.

' 40 grams of the mercaptan are caused to run drop by drop into hot dilute nitric acid, where-- by the chloroether sulphonic acid is formed by oxidation of the mercaptan group.

The acid solution is concentrated in the water cmmi-cmcnwmcmsoma there is added while stirring and cooling, a solution in benzene of mol. of lauric acid chloride in portions alternating withthe addition.

in portions of mol. of aqueous caustic Soda solution. After the reaction has been completed, the benzene is distilled off, the mixture is dried and extracted with alcohol and the alcoholic filtrate evaporated. There remains a substance which is mainly a body of the following composition:

Instead of methylamine there may be used in the above example ethylamine, aniline and the like. The lauric acid chloride may likewise be replaced by the equivalent quantity of abietic acid chloride.

(2) 40'grams of crystallizedsodium sulphite are dissolved in 200 grams of water and the whole is boiled with a mixture of 50 grams of beta-betadichlorodiethylether of the formula and 125 grams of alcohol until a test portion no longer has a. definitely perceptible smell of S02 on acidification. The duration of the reaction may be shortened by addition of substances which facilitate the reaction, (such as copper, copper salts or iodine salts) or by carrying out the reaction at elevatedftemperature (use of pressure vessels).

The mixture is then dried and the sodium salt of the chlorinated ether sulphonic acid ClCHaCHz-O-CHzCHaSOaNa is extracted by means of hot alcohol, The yield amounts to about 20 grams of sodium salt.

The subsequent transformation of the chlorether sulphonic acid obtained into the amino sulphonic acid and its acylation take place as indicated in Example 1.

The'dichlorodiethylether used in the above reaction may be replaced by other halogenated ethers, for instance, by beta-chloroethylchloromethylether of the formula C1CH2CH2O-CH2C1 by the methylether of glycerinedichlorohydrine of the formula cmca-cngocno-cmcl or the like.

(3) 285 parts of beta-methylamine-ether sodi-- um sulphate (63%, obtainable from beta-beta- 'dichlorodiethyletherby unilateral reaction with sulphite and exchange of the chlorine of the chloroether sulphonic .acid obtained for the methylamino-group, are dissolved together, with 'l5 parts of NaCl in 1100 parts of water. 256 parts of oleic acid chloride and 175'partsof caustic soda solution (40 B.) are their caused to run in simultaneously in the course of 4 hours, while stirring, at a temperature of 25-30 C. in such a manner that the reaction is always distinctly alkaline. for a short time to 50 C.-60 .C. and rendered feebly alkaline to phenolphthalein'by addition of hydrochloric acid. After drying, 650 parts of the reaction product containing 60% of a body having the following constitution are'obtained. The product is soluble in water to a clear solution, has a good dispersive power for Ca soap and may be used as washing agent.

We claim: I

Thereupon, the whole is heated 1. The process of producing sulphonic acids of 1 high molecular weight of aliphatic amino-ethers which comprises acylating the sulphonic acid of a lower aliphatic amino-ether, including its water-soluble salts with an acid of the group consisting of aliphatic carboxylic acids containing at least 10 carbon atoms, naphthenic acids and resin acids and an anhydride and halide, respectively,of such an acid.

2. The condensation products of the general formula:

RCON(R1) (R) ilRdsoltY wherein RCO stands for the acyl radical of a carboxylic acid selected from the group consist ing of aliphatic carboxylic acids-containing at least 10 carbon atoms, naphthenic acids and resin acids, R1 stands for a member of the group consisting of hydrogen, lower aliphatic hydrocarbon radicals and aromatic hydrocarbon radicals. R2 and R4 stand for lower saturated aliphatic hydrocarbon radicals. n stands for a member of the group consisting of the group 1,

2, and 3, Y stands for a member of the group consisting of hydrogen, alkali metal atoms and ammonium.

3. The condensation products of the general formula;

wherein RCO stands for the acyl radical of a carboxylic acid selected from the group consisting of aliphatic carboxylic acids containing at least 10 carbon atoms, naphthenic acids and resin acids, R1 stands for a member of the group consisting of hydrogen and hydrocarbon radicals,

R2 and R4 stand for lower saturated aliphatic hydrocarbon radicals, Y stands for a member of the group consisting of hydrogen, alkali metal atoms and ammonium.

4. The condensation products of the general formula:

RCON(Ri CHzCHaOCHzCHzSOaY wherein RCO stands for the acyl radical of a carboxylic acid selected from the group consisting of aliphatic carboxylic acids containing at least 10 carbon atoms, naphthenic acids and resin acids; R1 stands for a member of the group consisting of hydrogen and hydrocarbon, radicals; Y stands for a member of the group consisting of hydrogen, alkali metal atoms and ammonium.

5. The condensation product of the formula:

cunmcomcmi CHzCHzOH-aCHaSOaNa 6. The condensation product of the formula: CnHnGONwI-Ia) CIHaCHzOCHaCHaSOaNa.

EDMUND 'WALDMANN.

AUGUST CHWALA. 

